US8124574B2 - Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content - Google Patents

Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content Download PDF

Info

Publication number
US8124574B2
US8124574B2 US12/577,425 US57742509A US8124574B2 US 8124574 B2 US8124574 B2 US 8124574B2 US 57742509 A US57742509 A US 57742509A US 8124574 B2 US8124574 B2 US 8124574B2
Authority
US
United States
Prior art keywords
fatty
fatty acid
product
soap
acyl isethionate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US12/577,425
Other versions
US20110086789A1 (en
Inventor
Liang Sheng Tsaur
Virgilio Barba Villa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Conopco Inc
Original Assignee
Conopco Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Conopco Inc filed Critical Conopco Inc
Priority to US12/577,425 priority Critical patent/US8124574B2/en
Assigned to CONOPCO, INC., D/B/A/ UNILEVER reassignment CONOPCO, INC., D/B/A/ UNILEVER ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TSAUR, LIANG SHENG, VILLA, VIRGILIO BARBA
Priority to PCT/EP2010/064629 priority patent/WO2011045191A2/en
Priority to MX2012004296A priority patent/MX2012004296A/en
Priority to BR112012007254-4A priority patent/BR112012007254B1/en
Priority to EA201290196A priority patent/EA021866B1/en
Priority to ES10760681.6T priority patent/ES2529710T3/en
Priority to EP10760681.6A priority patent/EP2498747B1/en
Priority to CA2774287A priority patent/CA2774287C/en
Priority to JP2012533566A priority patent/JP5941408B2/en
Priority to CN201080045859.4A priority patent/CN102939071B/en
Priority to ARP100103671A priority patent/AR078567A1/en
Publication of US20110086789A1 publication Critical patent/US20110086789A1/en
Publication of US8124574B2 publication Critical patent/US8124574B2/en
Application granted granted Critical
Priority to ZA2012/01631A priority patent/ZA201201631B/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts

Definitions

  • the present invention is directed to liquid personal care skin or hair cleansing compositions comprising low levels of specific fatty isethionate product (e.g., less than 4% by wt., preferably less than 3% by wt.) and low overall fatty acid/fatty acid soap content (e.g., less than 4%).
  • low fatty isethionate product and low total fatty acid/soap are required to maintain superior lather relative to compositions otherwise identical or substantially identical (e.g., with regard to surfactants, emollients, polymers) except that they have higher overall fatty acid/fatty acid soap content (e.g., greater than 4%) or higher fatty isethionate product.
  • Amounts of long chain fatty acid/soap in the fatty isethionate product have been found critical for good mildness. Total amount of fatty acid/soap in the product are also critical.
  • Fatty acyl isethionates are anionic surfactants highly desirable in personal care skin or hair cleansing products, particularly in personal care products, because they lather well, are generally mild to the skin and have good emollient properties.
  • fatty acid isethionates are produced by esterification of fatty acids or by reaction of fatty acid chloride having carbon chain length of C 8 to C 20 with isethionate.
  • a typical fatty acyl isethionate surfactant product e.g., commercially sold or made surfactant product
  • % typically 5 to 40 wt. % free fatty acid, in addition to isethionate salts, typically at less than 5%, and trace amounts (less than 2 wt. %) of other impurities.
  • low total amounts of isethionate product it has been found critical that there be present minimum levels (greater than 15%, preferably greater than 20%) of fatty acid/fatty soap, as percent of the product, and in addition, that greater than 50% preferably greater than 60% of these fatty acid/soaps in the product be of chain length C 16 -C 20 (e.g., to preserve mildness).
  • levels of long chain in the product should be greater than 7.5%, preferably greater than 10%.
  • compositions comprising 3 to 45% by wt. fatty acyl isethionate product and 4 to 20% by wt. C 8 to C 20 total linear fatty acids and/or fatty soaps in the total composition.
  • fatty acids/fatty acid soaps of a length of greater than C 14 comprise 20 to 70% of total linear fatty acid/fatty acid soap and that ratio of total linear fatty acid/fatty soap to total synthetic surfactant was within defined ranges, applicants in that application were able to ensure consistent viscosity at both high and low temperatures.
  • That application was particularly concerned with utilizing fatty acyl isethionate products which might contain relatively large levels (e.g., at least 10% of product) of free fatty acid.
  • the present invention is directed to novel liquid cleansing composition comprising both less than 4% fatty isethionate product and less than 4%, preferably less than 3.8% total fatty acid/soap simultaneously. It is unpredictable and quite unexpected that when both these parameters are present at levels below 4%, the level of foam (in otherwise identical compositions) is significantly higher relative to foam level of compositions where either level of isethionate product is greater than or equal to 4% and/or level of total fatty acid/fatty acid soap is greater than or equal to 4%. Further, both the total level of fatty acid/soap in the product and the amount of long chain fatty acid/soap in the isethionate product component has been found critical.
  • liquid cleansing composition comprising:
  • the ratio of fatty acyl isethionate surfactant of item (a) to total synthetic surfactants in item (b) is less than 1 ⁇ 2, preferably less than 1 ⁇ 3
  • foam volume (measured by cylinder shake method) at fatty acid/soap level less than 4% is better by at least about 10%, preferably about 15% relative to identical composition comprising greater than or equal to 4% fatty acid/soap.
  • pH of the compositions typically is from about 4.5 to 7.6, preferably 5.0 to 7.2.
  • the invention relates to a process for making such composition.
  • the present invention relates to liquid compositions which contain fatty acid isethionate product, wherein the product contains 15 to 50%, preferably greater than or equal to 20% to 50% of free fatty acids/fatty soaps, and wherein greater than 50%, preferably greater than 60% of the free fatty acid/soaps in the product is chain length C 16 to C 20 and greater than or equal to 20%, preferably greater than 25% of the fatty acyl isethionate products are chain length ⁇ C 16 .
  • use of such product is beneficial because of its mildness and lather.
  • composition comprising:
  • the ratio of fatty acyl isethionate surfactant of item (a) to total synthetic surfactants in item (b) is less than 1 ⁇ 2, preferably less than 1 ⁇ 3.
  • foam volume (measured by cylinder shake method) at fatty acid/soap level less than 4% is better by at least 10%, preferably about 15% relative to identical composition comprising greater than or equal to 4% total fatty acids/soap.
  • the pH of the composition is typically is from about 4.5 to 7.6, preferably 5.0 to 7.2.
  • a fatty acyl isethionate “product” comprises (in addition to other components) both pure fatty acyl isethionate surfactant (e.g., 40 to 80%) as well as free fatty acid and/or fatty acid salt (e.g., 15 to 50%).
  • compositions of the invention comprise 0.3, preferably 0.5 to less than 4% by wt. fatty acyl isethionate surfactant product comprising 40 to 80% fatty isethionate and 15%, possibly 20% minimum to 50% of free fatty acids/fatty soaps in that product.
  • fatty acyl isethionate surfactant product comprising 40 to 80% fatty isethionate and 15%, possibly 20% minimum to 50% of free fatty acids/fatty soaps in that product.
  • greater than 20%, preferably greater than 25% of the fatty acyl isethionate are of chain length ⁇ C 16 and greater than 50%, preferably greater than 60% of the free fatty acid/soap are of chain length C 16 to C 20 .
  • a product containing at least 15% fatty acids/soaps and greater than 50% C 16 to C 20 would have greater than 7.5% C 16 to C 20 fatty acid/soaps in the fatty acyl isethionate product.
  • Fatty acyl isethionate surfactant are typically prepared by the reaction of an isethionates salt such as alkali metal isethionates and an aliphatic fatty acid having 8 to 20 carbon atoms and Iodine Value (measuring degree of unsaturation) of less than 20 g, for example: HOR 1 SO 3 M+RCOOH ⁇ RCOOR 1 SO 3 H
  • R 1 is an aliphatic hydrocarbon radical containing 2 to 4 carbons
  • the resulting fatty acyl isethionate product can be a mixture of 40 to 80% by weight of fatty acyl isethionates and 50 to about 15 wt %, typically 40 to 20 wt % of free fatty acids, in addition to isethionates salts which are present typically at less than 5 wt %, and traces (less than 2 wt. %) of other impurities.
  • a mixture of aliphatic fatty acids is used for the preparation of commercial fatty acyl isethionates surfactants and resulting fatty acyl isethionate surfactants (e.g., resulting from reaction of alkali metal isethionate and aliphatic fatty acid) should have more than 20 wt %, preferably more than 25%, but no more than 40% wt., preferably 35% (on basis of fatty acyl isethionates reaction product) of fatty acyl group with 16 or greater carbon atoms to provide both lather and mildness of the resulting fatty acyl isethionate product.
  • These longer chain fatty acyl isethionate surfactants and fatty acids i.e. fatty acyl group and fatty acid with 16 or more carbons, form insoluble surfactant/fatty acid crystals typically in water at ambient temperatures. It is believed that these long chain fatty acyl isethionate surfactants together with free long chain fatty acids in the product contribute to the mildness of the fatty acyl isethionate product for skin cleanser applications.
  • Examples of commercial fatty acyl isethionate products that are particularly useful in the invention are DEFI flakes and Dove® cleansing bar noodles produced by Unilever.
  • DEFI Direct Esterification of Fatty Isethionate
  • flakes typically contain about 68 to 80 wt % of sodium fatty acyl isethionate and 15 to 30 wt % free fatty acid. More than 25 wt % and no more than 35% of fatty acyl group of the resulting fatty acyl isethionate have 16 to 18 carbon atoms; and more than 60wt % of the free fatty acid have 16 to 18 carbon atoms.
  • Dove® cleansing bar noodles are mixtures of DEFI flakes described above and long chain (mainly C 16 and C 18 ) fatty acid and fatty soap which contain about 40 to 55 wt % of fatty acyl isethionate and 30 to 40 wt % of fatty acid and fatty soap. Due to high level of long chain (16 or more carbons) fatty acyl isethionate and fatty acid, these preferred fatty acyl isethionate surfactant products are extremely mild and have very good emollient benefits to the skin. DEFI flake and Dove® cleansing bar noodles are the mostly widely used fatty acyl isethionate products in personal cleansing market especially personal cleansing bar. Incorporation of these mild fatty acyl isethionate products into personal cleansing liquid and achieving excellent lathering properties of the resulting liquids are extremely desirable.
  • DEFI flake and Dove® cleansing bar noodles are the mostly widely used fatty acyl isethionate products in personal cleansing market especially personal cleansing bar. Incorporation
  • a similar liquid prepared using Na cocoyl isethionate product (Jordopan CI) containing mainly short chain fatty acyl isethionate surfactant and low level (5-8%) of coco fatty acid did not show such negative effect on lather (comparative example C vs. C 2 ).
  • such composition would be less mild.
  • the amount of the preferred fatty acyl isethionate product added to the liquid composition of this invention is lower than 4wt %, preferably lower than 3 wt %.
  • a second component of the subject invention are surfactants selected from the groups consisting of anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants as described below.
  • level of co-surfactant the amount of acyl isethionate surfactant formed as part of the acyl isethionate product is not counted.
  • the amount of synthetic co-surfactant used in the present invention can be in the range of 3 to 15%, preferably 5 to 12 wt %; and its level is more than the amount of fatty acyl isethionate product added to the liquid of the invention.
  • the ratio of synthetic co-surfactant to fatty acyl isethionate surfactant is at least 2 to 1, preferably at least 3 to 1 and no more than 20 to 1.
  • the anionic surfactant may be, for example, an aliphatic sulfonate, such as a primary alkane (e.g., C 8 -C 22 ) sulfonate, primary alkane (e.g., C 8 -C 22 ) disulfonate, C 8 -C 22 alkene sulfonate, C 8 -C 22 hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate (AGS); or an aromatic sulfonate such as alkyl benzene sulfonate.
  • a primary alkane e.g., C 8 -C 22
  • primary alkane e.g., C 8 -C 22
  • disulfonate C 8 -C 22 alkene sulfonate
  • C 8 -C 22 hydroxyalkane sulfonate C 8 -C 22 hydroxyalkane sulfonate or al
  • the anionic may also be an alkyl sulfate (e.g., C 12 -C 18 alkyl sulfate) or alkyl ether sulfate (including alkyl glyceryl ether sulfates).
  • alkyl ether sulfates are those having the formula: RO(CH 2 CH 2 O) n SO 3 M
  • the anionic may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., C 6 -C 22 sulfosuccinates); alkyl and acyl taurates, alkyl and acyl sarcosinates, alkyl and acyl glycinates, alkyl sulfoacetates, C 8 -C 22 alkyl phosphates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates, C 8 -C 22 monoalkyl succinates and maleates, and branched acyl isethionates.
  • alkyl sulfosuccinates including mono- and dialkyl, e.g., C 6 -C 22 sulfosuccinates
  • alkyl and acyl taurates alkyl and acyl sarcosinates
  • anionics are ethoxylated carboxylates such as follows: R—(CH 2 CH 2 O) n CO 2 M
  • R is C 8 to C 20 alkyl; n is 1 to 20; and M is as defined above.
  • amido alkyl polypeptide carboxylates such as, for example, Monteine LCQ® by Seppic. Soap, i.e. neutralized fatty acid, is not considered as synthetic cosurfactant in this invention.
  • Zwitterionic surfactants are exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • a general formula for these compounds is:
  • Amphoteric detergents which may be used in this invention include at least one acid group. This may be a carboxylic or a sulphonic acid group. They include quaternary nitrogen and therefore are quaternary amido acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. They will usually comply with an overall structural formula:
  • R 1 is alkyl or alkenyl of 7 to 18 carbon atoms
  • R 2 and R 3 are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms;
  • n 2 to 4;
  • n 0 to 1;
  • X is alkylene of 1 to 3 carbon atoms optionally substituted with hydroxyl
  • Y is —CO 2 — or —SO 3 —
  • Amphoacetates and diamphoacetates are also intended to be covered in possible zwitterionic and/or amphoteric compounds which may be used.
  • the nonionic which may be used includes in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C 6 -C 22 ) phenols-ethylene oxide condensates, the condensation products of aliphatic (C 8 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • the nonionic may also be a sugar amide, such as a polysaccharide amide.
  • the surfactant may be one of the lactobionamides described in U.S. Pat. No. 5,389,279 to Au et al. which is hereby incorporated by reference or it may be one of the sugar amides described in U.S. Pat. No. 5,009,814 to Kelkenberg, hereby incorporated into the subject application by reference.
  • alkyl polysaccharides are alkylpolyglycosides of the formula R 2 O(C n H 2n O) t (glycosyl) x
  • composition of the invention comprises acyl isethionate product with mixture of anionic (e.g., alkoxylated sulfate such as alkali metal alkyl ether sulfate) and amphoteric (e.g., betaine).
  • anionic e.g., alkoxylated sulfate such as alkali metal alkyl ether sulfate
  • amphoteric e.g., betaine
  • isethionate product and anionic which comprises mixtures of sulfate and glycinate surfactants in combination with amphoteric.
  • the isethionate product may be used with alkyl ether sulfate alone; with amphoteric alone or with no co-surfactant at all.
  • Another essential ingredient of the present invention is combination of long chain and short chain linear fatty acids/fatty soaps in the liquid composition.
  • fatty acid for ease of discussion, it is noted that whenever the term fatty acid is used, it will be understood to encompass both fatty acid and fatty acid soaps.
  • Long chain fatty acid in this invention is defined as linear fatty acid with 16 to 20 carbons; and short chain fatty acid is linear fatty acid with 8 to 14 (preferably 10 to 12) carbons.
  • Fatty acids are used to increase the viscosity of the liquid composition at or above ambient temperature such that the viscosity of the liquid composition remains viscous enough to maintain its physical stability when stored at or above room temperature.
  • linear long chain fatty acids Besides increasing the liquid viscosity and storage stability, linear long chain fatty acids have good emollient properties and can enhance the mildness of synthetic surfactants.
  • Linear short chain fatty acids especially C 10 to C 12 are known to be effective to enhance the lather of a liquid composition. Mixture of long chain and short chain fatty acids is desired to make liquid which is stable, has good lather and is mild to the skin.
  • the liquid composition of this invention containing both low level of the preferred mild fatty acyl isethionate products and synthetic cosurfactants, it was found that a specific fatty acid mixture is required to achieve good lathering properties of the liquids.
  • the total amount of fatty acids has to be less than 4%, preferably less than 3.5%; and linear fatty acid with 16 or more carbons has to be less than 2.0%, preferably less than 1.5% and most preferably less than 1.0% in the total liquid composition of this invention.
  • the minimum amount of long chain fatty acids depends on the level of fatty acyl isethionate product in the liquid composition and its fatty acid content; it is preferred to have at least 0.1%, preferably 0.3% to achieve good lather and mildness.
  • Water soluble/dispersible polymers are an optional ingredient that is preferred to be included in the liquid composition of the invention.
  • the water soluble/or dispersible polymer can be cationic, anionic, amphoteric or nonionic polymer with molecular weight higher than 100,000 Dalton. These polymers are known to increase the viscosity and stability of liquid cleanser compositions, to enhance in-use and after-use skin sensory feels, and to enhance lather creaminess and lather stability.
  • the water soluble/dispersible polymers are required to stably suspend the added skin benefit agents.
  • Amount of polymers used can be in the range of 0.1 up to 10 wt % depending on the composition of the liquid cleansers.
  • water soluble/or dispersible polymers useful in the present invention include the carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, hydroxymethyl or carboxymethyl cellulose, methyl cellulose, ethyl cellulose, guar gum, gum karaya, gum tragacanth, gum arabic, gum acacia, gum agar, xanthan gum and mixtures thereof; modified and nonmodified starch granules with gelatinization temperature between 30 to 85° C.
  • carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, hydroxymethyl or carboxymethyl cellulose, methyl cellulose, ethyl cellulose, guar gum, gum karaya, gum tragacanth, gum arabic, gum acacia, gum agar, xant
  • cationic polymer such as modified polysaccharides including cationic guar available from Rhone Poulenc under the trade name Jaguar C13S, Jaguar C14S, Jaguar C17, or Jaguar C16, BF Guar C-17 from Lamberti; Aqua D4091 and D4051 from Aqualon; cationic modified cellulose such as UCARE Polymer JR 30 or JR 40 from Amerchol; N-Hance 3000, N-Hance 3196, N-Hance GPX 215 or N-Hance GPX 196 from Hercules; synthetic cationic polymer such as MerQuat 100, MerQuat 280, Merquat 281 and Merquat 550 by Nalco; cationic starches, e.g., StaLok® 100, 200, 300 and 400 made by Sta
  • Gel forming polymers such as modified or non-modified starch granules, xanthan gum, Carbopol, alkaline-soluble emulsion polymers and cationic guar gum such as Lamberti BF Guar C17, and cationic modified cellulose such as UCARE Polymer JR 30 or JR 40 are particularly preferred for this invention.
  • Water-soluble skin benefit agents another optional ingredient that is preferred to be included in the liquid compositions of the invention.
  • a variety of water-soluble skin benefit agents can be used and the level can be from 0 to 50 weight %, preferably 1 to 30%.
  • the materials include, but are not limited to, polyhydroxy alcohols such as glycerin, propylene glycol, dipropylene glycol, sorbitol, pantenol and sugar; urea, alpha-hydroxy acid and its salt such as glycolic or lactic acid; and low molecular weight polyethylene glycols with molecular weight less than 20,000.
  • Preferred water soluble skin benefit agents for use in the liquid composition are glycerin, sorbitol and propylene glycol.
  • the liquid cleansing composition of the invention also may comprise 0 to 40% by wt. benefit agent.
  • One class of ingredients are nutrients used to moisturize and strengthen, for example, the skin. These include:
  • a second type of skin benefit agent is a skin conditioner used to provide a moisturized feel to the skin.
  • Suitable skin conditioners include:
  • a third type of benefit agent is deep cleansing agents. These are defined here as ingredients that can either increase the sense of refreshment immediately after cleansing or can provide a sustained effect on skin problems that are associated with incomplete cleansing. Deep cleansing agents include:
  • benefit agents include antiaging compounds, sunscreens, and in lightening agents.
  • hydrophobic polymers of the type describe in U.S. Pat. No. 5,817,609 to He et al. may be employed, which is incorporated by reference into the subject application.
  • compositions should be between 4.5 to 7.6, preferably 5.0 to 7.2.
  • the compositions should also be physically phase stable at room temperature and 40° C. for at least two 2 weeks.
  • compositions of the invention may include 0 to 10% by wt. optional ingredients as follows:
  • Perfumes such as tetra sodium ethylenediaminetetraacetate (EDTA), EHDP or mixtures in an amount of 0.01 to 1%, preferably 0.01 to 0.05%; and coloring agents, opacifiers and pearlizers such as zinc striate, magnesium stearate, T 1 O 2 , EGMS (ethylene glycol monostearate) or Lytron 621 (Styrene/Acrylate copolymer); all of which are useful in enhancing the appearance or cosmetic properties of the product.
  • EDTA tetra sodium ethylenediaminetetraacetate
  • EHDP ethylenediaminetetraacetate
  • coloring agents, opacifiers and pearlizers such as zinc striate, magnesium stearate, T 1 O 2 , EGMS (ethylene glycol monostearate) or Lytron 621 (Styrene/Acrylate copolymer); all of which are useful in enhancing the appearance or cosmetic properties of the product.
  • compositions may further comprise antimicrobials such as 2-hydroxy-4,2′4′ trichlorodiphenyl ether (DP300); preservatives such as dimethyloldimethylhydantoin (Glydant XL 1000), parabens, sorbic acid etc.
  • antimicrobials such as 2-hydroxy-4,2′4′ trichlorodiphenyl ether (DP300); preservatives such as dimethyloldimethylhydantoin (Glydant XL 1000), parabens, sorbic acid etc.
  • Antioxidants such as, for example, butylated hydroxytoluene (BHT) may be used advantageously in amounts of about 0.01% or higher if appropriate.
  • BHT butylated hydroxytoluene
  • Polyethylene glycols as conditioners which may be used include:
  • Polyox WSR-25 PEG 14M, Polyox WSR-N-60K PEG 45M, or Polyox WSR-N-750 PEG 7M are examples of Polyox WSR-25 PEG 14M, Polyox WSR-N-60K PEG 45M, or Polyox WSR-N-750 PEG 7M.
  • exfoliants such as polyoxyethylene beads, walnut shells and apricot seeds.
  • Example of this invention 1 2 3 — — — — — — — Comparative example F — — A B C C2 D E (Control) Isethionate product A 2 2 2 2 2 4 2 2 — Na cocoyl isethionate — — — — — — 4 — — — Jordapon CI Na cocoamido propyl 4 4 4 4 4 4 4 4 4 betaine Na cocoyl glycinate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Na laury
  • Example of this invention 4 — 5 — 6 7 — — Comparative example — G — H — — I J Isethionate product A 2 2 1 1 2 2 2 2 Na cocoamido propyl 0 0 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 betaine Na cocoyl glycinate 2.7 2.7 4 4 4 4 4 Na laurylsarcosinate — — 1 1 1 1 1 Na laurylethoxyl sulfate 5.0 5.0 — — — — — Lauric acid 2.5 2.5 1.6 3.1 3.0 2.0 3.0 1.5 ASAD* — 0.8 0 0.6 — 0.6 1.5 Glycerin 1.15 1.15 10 10 6 6 6 6 Cationic polymer — — 0.4 0.4 0.2 0.2 0.2 0.2 Lamberti BF Guar C17 Sunflower seed oil 1 1 — — — — — — — — Petrolatum
  • Table 1 and Table 2 All examples in Table 1 and Table 2 were prepared by mixing all the ingredients except petrolatum, sunflower seed oil, perfume, glydant and EDTA at 70 to 75° C. for 30 to 50 minutes until all the solid ingredients such as isethionate product A and fatty acids dissolved to form an uniform mixture. Molten petrolatum and sunflower seed oil were added during cooling. Perfume and glydant plus (a hydantoin preservative) were added after the liquid was cooled below 40° C. Isethionate product A are fatty acyl isethionate products manufactured by Unilever.
  • Comparative example F (Control), a liquid without any fatty acyl isethionate product, was prepared as control for lather volume comparison. It can be seen clearly in Examples 1, 2 and 3 versus comparative F that addition of fatty acyl isethionate product at low level (2% isethionate product A) enhances foam volume (e.g., from 37.1 to about 42 on average). However, when higher level, i.e. 4%, of the preferred fatty acyl isethionate product is added (Comparative example C), foam volume is depressed (31.4) compared to comparative F which contains no fatty acyl isethionate product. This happens only for the preferred fatty acyl isethionate product of this invention.

Abstract

The present invention relates to liquid personal care composition comprising both low levels of specific fatty isethionate product (e.g., less than 4%) and low overall fatty acid content (less than 4%) which, quite surprisingly, maintain excellent foaming profile relative to identical composition having high overall fatty acid content.

Description

FIELD OF THE INVENTION
The present invention is directed to liquid personal care skin or hair cleansing compositions comprising low levels of specific fatty isethionate product (e.g., less than 4% by wt., preferably less than 3% by wt.) and low overall fatty acid/fatty acid soap content (e.g., less than 4%). Surprisingly and unpredictably, both low fatty isethionate product and low total fatty acid/soap are required to maintain superior lather relative to compositions otherwise identical or substantially identical (e.g., with regard to surfactants, emollients, polymers) except that they have higher overall fatty acid/fatty acid soap content (e.g., greater than 4%) or higher fatty isethionate product. Amounts of long chain fatty acid/soap in the fatty isethionate product have been found critical for good mildness. Total amount of fatty acid/soap in the product are also critical.
BACKGROUND OF THE INVENTION
Fatty acyl isethionates (e.g., cocoyl isethionates) are anionic surfactants highly desirable in personal care skin or hair cleansing products, particularly in personal care products, because they lather well, are generally mild to the skin and have good emollient properties. Typically, fatty acid isethionates are produced by esterification of fatty acids or by reaction of fatty acid chloride having carbon chain length of C8 to C20 with isethionate. A typical fatty acyl isethionate surfactant product (e.g., commercially sold or made surfactant product) contains about 40 to 95 wt. % fatty acyl isethionate, and 0 to 50 wt. %, typically 5 to 40 wt. % free fatty acid, in addition to isethionate salts, typically at less than 5%, and trace amounts (less than 2 wt. %) of other impurities. In the present invention, since low total amounts of isethionate product are used, it has been found critical that there be present minimum levels (greater than 15%, preferably greater than 20%) of fatty acid/fatty soap, as percent of the product, and in addition, that greater than 50% preferably greater than 60% of these fatty acid/soaps in the product be of chain length C16-C20 (e.g., to preserve mildness). Specifically levels of long chain in the product (calculated by multiplying total fatty acid/soap in the product by the % of long chain) should be greater than 7.5%, preferably greater than 10%.
In a previous application, U.S. Ser. No. 11/958,471, applicants claimed the use of compositions comprising 3 to 45% by wt. fatty acyl isethionate product and 4 to 20% by wt. C8 to C20 total linear fatty acids and/or fatty soaps in the total composition. By ensuring that fatty acids/fatty acid soaps of a length of greater than C14 comprise 20 to 70% of total linear fatty acid/fatty acid soap and that ratio of total linear fatty acid/fatty soap to total synthetic surfactant was within defined ranges, applicants in that application were able to ensure consistent viscosity at both high and low temperatures.
That application was particularly concerned with utilizing fatty acyl isethionate products which might contain relatively large levels (e.g., at least 10% of product) of free fatty acid.
In that reference, never was there used less than 4% by wt. of a fatty acid isethionate product (4% used in Example 13) and in that example, there was also used at least 4% free fatty acid (e.g., 4% lauric acid) and certainly more since there is also some fatty acid present in the fatty acyl isethionate product itself.
It was never contemplated to use low levels of acyl isethionate product and low levels of total fatty acid because the expectation of one skilled in the art would be that use of less fatty acyl isethionate product would lead to lower foam values. Quite unpredictably, however, applicants have found that it is possible to use lower levels of fatty acyl isethionate product (maintaining benefits of such products at lower cost) while retaining good foam, but only if the level of total free fatty acid/fatty soap is maintained below 4% and the total level of C16 to C20 fatty acid/fatty soaps is in the range of 0.1 to 2%, preferably 0.3 to 1.5% in order to provide both mildness and good lather. Thus, counterintuitively, applicants are able to use both less acyl isethionate product and less free fatty acid (indeed unpredictably applicants have found they must use less fatty acid) in order to ensure good foaming.
Applicants are aware of no reference in the art which teach or suggest low levels of acyl isethionate product in combination with ceiling levels of free fatty acid/soap (from combined acyl isethionate product and free fatty acid/soap in total composition) in order to ensure superior foaming relative to otherwise identical compositions having higher total free fatty acid/soap.
Other references which may be broadly related include:
U.S. Pat. No. 5,415,810 to Lee; U.S. Pat. No. 5,739,365 to Brody; U.S. Publication No. 2004/0274863; U.S. Pat. Nos. 5,952,286 and 6,077,816 to Puwada; U.S. Pat. Nos. 5,132,037, 5,234,619 and 5,290,471 to Greene et al.
Applicants have also filed, in addition to U.S. Ser. No. 11/958,471 noted above, additional applications in this general area as noted:
Ser. No. 11/613,617
Ser. No. 11/613,696
Ser. No. 11/613,666
Ser. No. 11/850,159
Ser. No. 12/235,955.
As indicated, none of the references discloses 0.1 to less than 4%, preferably 0.5 to less than 4%, preferably 0.5 to 3.8% by wt. fatty acid isethionate product which must be used in combination with 0.1 to less than 4%, preferably 0.3 to 3.8% total free fatty acid/soap (from combined product and free fatty acid/soap); and where the total amount of long chain C16 to C20 fatty acid/soap is in the range of 0.1 to 2%, preferably, 0.3 to 1.5% in the liquid composition of the invention. Moreover, none of the references recognizes that, only when total free fatty acid/soap is maintained at these levels will foam be unexpectedly enhanced in otherwise identical (e.g., in terms of co-surfactant, emollient, cationic polymer, etc.) compositions. This is counterintuitive because one would want to use more of fatty acid isethionate product to enhance foam.
As indicated, applicants have been able to achieve this goal at least in part (while retaining good mildness) by utilizing isethionate products which have relatively large amounts of free fatty acid/soap (greater than 15%) of which C16 to C20 comprise >50% such that total levels of long chain length is greater than 7.5% preferably greater than 10% of the product.
BRIEF SUMMARY OF THE INVENTION
The present invention is directed to novel liquid cleansing composition comprising both less than 4% fatty isethionate product and less than 4%, preferably less than 3.8% total fatty acid/soap simultaneously. it is unpredictable and quite unexpected that when both these parameters are present at levels below 4%, the level of foam (in otherwise identical compositions) is significantly higher relative to foam level of compositions where either level of isethionate product is greater than or equal to 4% and/or level of total fatty acid/fatty acid soap is greater than or equal to 4%. Further, both the total level of fatty acid/soap in the product and the amount of long chain fatty acid/soap in the isethionate product component has been found critical.
More specifically, the subject invention comprises liquid cleansing composition comprising:
    • (a) 0.3 to less than 4% fatty acid isethionate product, wherein said product comprises 40 to 80% fatty acyl isethionate as well as 15 to 50%, preferably greater than or equal to 20% to 50% of free fatty acids and/or fatty soaps in that product and wherein (e.g., to ensure mildness of final composition) greater than 20%, preferably greater than 25% of the fatty acyl isethionate are of chain length greater than or equal to C16, and greater than 50%, preferably greater than 60% of the free fatty acid/soap are of chain length ≧C16 (e.g., C16 to C24, preferably C16 to C20);
    • (b) 3 to 15% preferably 5 to 15% by wt. of a co-surfactant selected from the group consisting of anionic surfactant (excluding fatty acyl isethionate component of the fatty acyl isethionate product of (a)), amphoteric surfactant, nonionic surfactant and mixtures thereof;
    • (c) 0.1 to less than 4% C8 to C20 total linear free fatty acids/fatty soaps (comprising both free fatty acids/fatty soaps in the fatty acyl isethionate product of (a) as well as those added separately in composition) wherein the total amount of linear C16 to C20 fatty acids is less than 2%, preferably less than 1.5%, but at least 0.1%, preferably 0.3%.
Preferably, the ratio of fatty acyl isethionate surfactant of item (a) to total synthetic surfactants in item (b) is less than ½, preferably less than ⅓
Preferably, foam volume (measured by cylinder shake method) at fatty acid/soap level less than 4% is better by at least about 10%, preferably about 15% relative to identical composition comprising greater than or equal to 4% fatty acid/soap.
pH of the compositions typically is from about 4.5 to 7.6, preferably 5.0 to 7.2.
In a second embodiment, the invention relates to a process for making such composition.
These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilized in any other aspect of the invention. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Other than in the experimental example, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term “about”. Similarly, all percentages are weight/weight percentages of the total composition unless otherwise indicated. Numerical ranges expressed in the format “from x to y” are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format “from x to y” it is understood that all ranges combining the different endpoints are also contemplated. Further in specifying the range of concentration, it is noted that any particular upper concentration can be associated with any particular lower concentration. Where the term “comprising” is used in the specification or clams, it is not intended to exclude any terms, steps or features not specifically recited. For the avoidance of doubt, the word “comprising” is intended to mean “including” but not necessarily “consisting of” or “composed of”. In other words, the listed steps, options, or alternatives need not be exhaustive. All temperatures are in degrees Celsius (° C.) unless specific otherwise. All measurements are in SI units unless specified otherwise. All documents cited are—in relevant part—incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to liquid compositions which contain fatty acid isethionate product, wherein the product contains 15 to 50%, preferably greater than or equal to 20% to 50% of free fatty acids/fatty soaps, and wherein greater than 50%, preferably greater than 60% of the free fatty acid/soaps in the product is chain length C16 to C20 and greater than or equal to 20%, preferably greater than 25% of the fatty acyl isethionate products are chain length ≧C16. On the one hand, use of such product is beneficial because of its mildness and lather. On the other hand, it would be beneficial to obtain the benefits of the use of such products while minimizing costs by using less of the product. Using less, however, would be expected to result in weak foam values. Unexpectedly, applicants have found that less can be used, not by incorporating additional free fatty acid but, quite to the contrary, by keeping total amount of free fatty acid/fatty acid soap (from combined amounts of product and free fatty acid/soap in the composition) below defined critical values.
More specifically, the present invention relates to composition comprising:
    • (a) 0.3 to less than 4% by wt. fatty acyl isethionate product, wherein said product comprises 40 to 80% fatty acyl isethionate as well as 15 to 50%, preferably greater than or equal to 20% to 50% free fatty acids and/or fatty soaps in that product and wherein (e.g., to ensure mildness of final compositions), greater than 20%, preferably greater than 25% of fatty acyl isethionate are of chain length ≧C16 and greater than 50%, preferably greater than 60% of free fatty acid/soap are of chain length ≧C16 (e.g., C16 to C24, preferably C16 to C20);
    • (b) 3 to 15%, preferably 5 to 12% by wt. of a co-surfactant selected from the group consisting of anionic surfactant (excluding fatty acyl isethionate component of the fatty acyl isethionate product of (a)), amphoteric surfactant, nonionic surfactant, and mixtures thereof;
    • (c) 0.1 to less than 4% C8 to C20 total linear free fatty acids/fatty soap (comprising both free fatty acids/fatty soaps in fatty acid product (a) as well as those added separately in composition), wherein the total amount of linear C16 to C20 fatty acids is less than 2%, preferably less than 1.5%, and at least 0.1%, preferably 0.3%.
Preferably, the ratio of fatty acyl isethionate surfactant of item (a) to total synthetic surfactants in item (b) is less than ½, preferably less than ⅓.
Preferably, foam volume (measured by cylinder shake method) at fatty acid/soap level less than 4% is better by at least 10%, preferably about 15% relative to identical composition comprising greater than or equal to 4% total fatty acids/soap.
The pH of the composition is typically is from about 4.5 to 7.6, preferably 5.0 to 7.2.
Definition
For purposes of this invention, a fatty acyl isethionate “product” comprises (in addition to other components) both pure fatty acyl isethionate surfactant (e.g., 40 to 80%) as well as free fatty acid and/or fatty acid salt (e.g., 15 to 50%).
The compositions of the invention comprise 0.3, preferably 0.5 to less than 4% by wt. fatty acyl isethionate surfactant product comprising 40 to 80% fatty isethionate and 15%, possibly 20% minimum to 50% of free fatty acids/fatty soaps in that product. In addition, greater than 20%, preferably greater than 25% of the fatty acyl isethionate are of chain length ≧C16 and greater than 50%, preferably greater than 60% of the free fatty acid/soap are of chain length C16 to C20.
Thus, for example, a product containing at least 15% fatty acids/soaps and greater than 50% C16 to C20 would have greater than 7.5% C16 to C20 fatty acid/soaps in the fatty acyl isethionate product.
Fatty acyl isethionate surfactant are typically prepared by the reaction of an isethionates salt such as alkali metal isethionates and an aliphatic fatty acid having 8 to 20 carbon atoms and Iodine Value (measuring degree of unsaturation) of less than 20 g, for example:
HOR1SO3M+RCOOH→RCOOR1SO3H
where R1 is an aliphatic hydrocarbon radical containing 2 to 4 carbons;
    • M is alkali metal cation or metal ion (e.g., sodium, magnesium, potassium, lithium), ammonium or substituted ammonium cation or other counterion; and
    • R is an aliphatic hydrocarbon radical having 7 to 24, preferably 8 to 22 carbons.
Depending on the processing conditions used, the resulting fatty acyl isethionate product can be a mixture of 40 to 80% by weight of fatty acyl isethionates and 50 to about 15 wt %, typically 40 to 20 wt % of free fatty acids, in addition to isethionates salts which are present typically at less than 5 wt %, and traces (less than 2 wt. %) of other impurities. Preferably, a mixture of aliphatic fatty acids is used for the preparation of commercial fatty acyl isethionates surfactants and resulting fatty acyl isethionate surfactants (e.g., resulting from reaction of alkali metal isethionate and aliphatic fatty acid) should have more than 20 wt %, preferably more than 25%, but no more than 40% wt., preferably 35% (on basis of fatty acyl isethionates reaction product) of fatty acyl group with 16 or greater carbon atoms to provide both lather and mildness of the resulting fatty acyl isethionate product. These longer chain fatty acyl isethionate surfactants and fatty acids, i.e. fatty acyl group and fatty acid with 16 or more carbons, form insoluble surfactant/fatty acid crystals typically in water at ambient temperatures. It is believed that these long chain fatty acyl isethionate surfactants together with free long chain fatty acids in the product contribute to the mildness of the fatty acyl isethionate product for skin cleanser applications.
Examples of commercial fatty acyl isethionate products that are particularly useful in the invention are DEFI flakes and Dove® cleansing bar noodles produced by Unilever. DEFI (Direct Esterification of Fatty Isethionate) flakes typically contain about 68 to 80 wt % of sodium fatty acyl isethionate and 15 to 30 wt % free fatty acid. More than 25 wt % and no more than 35% of fatty acyl group of the resulting fatty acyl isethionate have 16 to 18 carbon atoms; and more than 60wt % of the free fatty acid have 16 to 18 carbon atoms. Dove® cleansing bar noodles are mixtures of DEFI flakes described above and long chain (mainly C16 and C18) fatty acid and fatty soap which contain about 40 to 55 wt % of fatty acyl isethionate and 30 to 40 wt % of fatty acid and fatty soap. Due to high level of long chain (16 or more carbons) fatty acyl isethionate and fatty acid, these preferred fatty acyl isethionate surfactant products are extremely mild and have very good emollient benefits to the skin. DEFI flake and Dove® cleansing bar noodles are the mostly widely used fatty acyl isethionate products in personal cleansing market especially personal cleansing bar. Incorporation of these mild fatty acyl isethionate products into personal cleansing liquid and achieving excellent lathering properties of the resulting liquids are extremely desirable.
It was surprising to find that addition of such preferred fatty acyl isethionate product to a liquid containing synthetic cosurfactants (described below) as the main surfactant has a big impact on lather of the resulting liquids. This is shown in examples of this invention. At low level of the fatty acyl isethionate product, the lather of the liquid was enhanced due to addition of extra surfactant (Example 1 vs. comparative example E where lather range from 37.1 to 43.4 when using 2% of isethionate product within definition of invention). However, at a level of 4% (comparative example C), the lather unexpectedly decreased compared to the liquid without the fatty acyl isethionate product (comparative example E). A similar liquid prepared using Na cocoyl isethionate product (Jordopan CI) containing mainly short chain fatty acyl isethionate surfactant and low level (5-8%) of coco fatty acid did not show such negative effect on lather (comparative example C vs. C2). However, especially given low levels of >C16 total fatty acids and fatty acyl isethionate surfactant, such composition would be less mild. To both achieve mildness and maintain or enhance lather of liquids containing low level of synthetic surfactants, the amount of the preferred fatty acyl isethionate product added to the liquid composition of this invention is lower than 4wt %, preferably lower than 3 wt %.
Synthetic Co-Surfactants
A second component of the subject invention are surfactants selected from the groups consisting of anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants as described below. When determining level of co-surfactant, the amount of acyl isethionate surfactant formed as part of the acyl isethionate product is not counted. The amount of synthetic co-surfactant used in the present invention can be in the range of 3 to 15%, preferably 5 to 12 wt %; and its level is more than the amount of fatty acyl isethionate product added to the liquid of the invention. The ratio of synthetic co-surfactant to fatty acyl isethionate surfactant is at least 2 to 1, preferably at least 3 to 1 and no more than 20 to 1.
The anionic surfactant may be, for example, an aliphatic sulfonate, such as a primary alkane (e.g., C8-C22) sulfonate, primary alkane (e.g., C8-C22) disulfonate, C8-C22 alkene sulfonate, C8-C22 hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate (AGS); or an aromatic sulfonate such as alkyl benzene sulfonate.
The anionic may also be an alkyl sulfate (e.g., C12-C18 alkyl sulfate) or alkyl ether sulfate (including alkyl glyceryl ether sulfates). Among the alkyl ether sulfates are those having the formula:
RO(CH2CH2O)nSO3M
    • wherein R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 16 carbons, n has an average value of greater than at least 0.5, preferably between 2 and 3; and M is a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium. Ammonium and sodium lauryl ether sulfates are preferred.
The anionic may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., C6-C22 sulfosuccinates); alkyl and acyl taurates, alkyl and acyl sarcosinates, alkyl and acyl glycinates, alkyl sulfoacetates, C8-C22 alkyl phosphates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates, C8-C22 monoalkyl succinates and maleates, and branched acyl isethionates.
Another class of anionics are ethoxylated carboxylates such as follows:
R—(CH2CH2O)nCO2M
wherein R is C8 to C20 alkyl; n is 1 to 20; and M is as defined above.
Another carboxylate which can be used is amido alkyl polypeptide carboxylates such as, for example, Monteine LCQ® by Seppic. Soap, i.e. neutralized fatty acid, is not considered as synthetic cosurfactant in this invention.
Zwitterionic surfactants are exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is:
Figure US08124574-20120228-C00001
    • wherein R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus atom; R4 is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Amphoteric detergents which may be used in this invention include at least one acid group. This may be a carboxylic or a sulphonic acid group. They include quaternary nitrogen and therefore are quaternary amido acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. They will usually comply with an overall structural formula:
Figure US08124574-20120228-C00002
where R1 is alkyl or alkenyl of 7 to 18 carbon atoms;
R2 and R3 are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms;
n is 2 to 4;
m is 0 to 1;
X is alkylene of 1 to 3 carbon atoms optionally substituted with hydroxyl, and
Y is —CO2— or —SO3—
Amphoacetates and diamphoacetates are also intended to be covered in possible zwitterionic and/or amphoteric compounds which may be used.
The nonionic which may be used includes in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6-C22) phenols-ethylene oxide condensates, the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
The nonionic may also be a sugar amide, such as a polysaccharide amide. Specifically, the surfactant may be one of the lactobionamides described in U.S. Pat. No. 5,389,279 to Au et al. which is hereby incorporated by reference or it may be one of the sugar amides described in U.S. Pat. No. 5,009,814 to Kelkenberg, hereby incorporated into the subject application by reference.
Other surfactants which may be used are described in U.S. Pat. No. 3,723,325 to Parran Jr. and alkyl polysaccharide nonionic surfactants as disclosed in U.S. Pat. No. 4,565,647 to Llenado, both of which are also incorporated into the subject application by reference.
Preferred alkyl polysaccharides are alkylpolyglycosides of the formula
R2O(CnH2nO)t(glycosyl)x
    • wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 0 to 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from 1.3 to about 10, preferably from 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
Other surfactants which may be used are described in U.S. Pat. No. 3, 723,325 to Parran Jr. and “Surface Active Agents and Detergents” (Vol. I & II) by Schwartz, Perry & Berch, both of which is also incorporated into the subject application by reference.
One preferred composition of the invention comprises acyl isethionate product with mixture of anionic (e.g., alkoxylated sulfate such as alkali metal alkyl ether sulfate) and amphoteric (e.g., betaine). Another preferred embodiment includes isethionate product and anionic which comprises mixtures of sulfate and glycinate surfactants in combination with amphoteric. In other embodiments, the isethionate product may be used with alkyl ether sulfate alone; with amphoteric alone or with no co-surfactant at all.
Fatty Acids
Another essential ingredient of the present invention is combination of long chain and short chain linear fatty acids/fatty soaps in the liquid composition. For ease of discussion, it is noted that whenever the term fatty acid is used, it will be understood to encompass both fatty acid and fatty acid soaps. Long chain fatty acid in this invention is defined as linear fatty acid with 16 to 20 carbons; and short chain fatty acid is linear fatty acid with 8 to 14 (preferably 10 to 12) carbons. Fatty acids are used to increase the viscosity of the liquid composition at or above ambient temperature such that the viscosity of the liquid composition remains viscous enough to maintain its physical stability when stored at or above room temperature. Besides increasing the liquid viscosity and storage stability, linear long chain fatty acids have good emollient properties and can enhance the mildness of synthetic surfactants. Linear short chain fatty acids especially C10 to C12, are known to be effective to enhance the lather of a liquid composition. Mixture of long chain and short chain fatty acids is desired to make liquid which is stable, has good lather and is mild to the skin. For the liquid composition of this invention containing both low level of the preferred mild fatty acyl isethionate products and synthetic cosurfactants, it was found that a specific fatty acid mixture is required to achieve good lathering properties of the liquids. As shown in the examples of this invention, to have good lather the total amount of fatty acids has to be less than 4%, preferably less than 3.5%; and linear fatty acid with 16 or more carbons has to be less than 2.0%, preferably less than 1.5% and most preferably less than 1.0% in the total liquid composition of this invention. The minimum amount of long chain fatty acids depends on the level of fatty acyl isethionate product in the liquid composition and its fatty acid content; it is preferred to have at least 0.1%, preferably 0.3% to achieve good lather and mildness.
Water Soluble/Dispersible Polymers
Water soluble/dispersible polymers are an optional ingredient that is preferred to be included in the liquid composition of the invention. The water soluble/or dispersible polymer can be cationic, anionic, amphoteric or nonionic polymer with molecular weight higher than 100,000 Dalton. These polymers are known to increase the viscosity and stability of liquid cleanser compositions, to enhance in-use and after-use skin sensory feels, and to enhance lather creaminess and lather stability. When water insoluble skin benefit agent is used in this invention, the water soluble/dispersible polymers are required to stably suspend the added skin benefit agents. Amount of polymers used can be in the range of 0.1 up to 10 wt % depending on the composition of the liquid cleansers.
Examples of water soluble/or dispersible polymers useful in the present invention include the carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, hydroxymethyl or carboxymethyl cellulose, methyl cellulose, ethyl cellulose, guar gum, gum karaya, gum tragacanth, gum arabic, gum acacia, gum agar, xanthan gum and mixtures thereof; modified and nonmodified starch granules with gelatinization temperature between 30 to 85° C. and pregelatinized cold water soluble starch; polyacrylate; Carbopols; alkaline soluble emulsion polymer such as Aculyn 28, Aculyn 22 or Carbopol Aqua SF1; cationic polymer such as modified polysaccharides including cationic guar available from Rhone Poulenc under the trade name Jaguar C13S, Jaguar C14S, Jaguar C17, or Jaguar C16, BF Guar C-17 from Lamberti; Aqua D4091 and D4051 from Aqualon; cationic modified cellulose such as UCARE Polymer JR 30 or JR 40 from Amerchol; N-Hance 3000, N-Hance 3196, N-Hance GPX 215 or N-Hance GPX 196 from Hercules; synthetic cationic polymer such as MerQuat 100, MerQuat 280, Merquat 281 and Merquat 550 by Nalco; cationic starches, e.g., StaLok® 100, 200, 300 and 400 made by Staley Inc.; cationic galactomannans based on guar gum of Galactasol 800 series by Henkel, Inc.; Quadrosoft Um-200; and Polyquaternium-24.
Gel forming polymers such as modified or non-modified starch granules, xanthan gum, Carbopol, alkaline-soluble emulsion polymers and cationic guar gum such as Lamberti BF Guar C17, and cationic modified cellulose such as UCARE Polymer JR 30 or JR 40 are particularly preferred for this invention.
Water Soluble Skin Benefit Agents
Water-soluble skin benefit agents another optional ingredient that is preferred to be included in the liquid compositions of the invention. A variety of water-soluble skin benefit agents can be used and the level can be from 0 to 50 weight %, preferably 1 to 30%. The materials include, but are not limited to, polyhydroxy alcohols such as glycerin, propylene glycol, dipropylene glycol, sorbitol, pantenol and sugar; urea, alpha-hydroxy acid and its salt such as glycolic or lactic acid; and low molecular weight polyethylene glycols with molecular weight less than 20,000. Preferred water soluble skin benefit agents for use in the liquid composition are glycerin, sorbitol and propylene glycol.
The liquid cleansing composition of the invention also may comprise 0 to 40% by wt. benefit agent.
One class of ingredients are nutrients used to moisturize and strengthen, for example, the skin. These include:
    • a) vitamins such as vitamin A and E, and vitamin alkyl esters such as vitamin C alkyl esters;
    • b) lipids such as cholesterol, cholesterol esters, lanolin, creaminess, sucrose esters, and pseudo-ceramides;
    • c) liposome forming materials such as phospholipids, and suitable amphophilic molecules having two long hydrocarbon chains;
    • d) essential fatty acids, poly unsaturated fatty acids, and sources of these materials;
    • e) triglycerides of unsaturated fatty acids such as sunflower oil, primrose oil avocado oil, almond oil;
    • f) vegetable butters formed from mixtures of saturated and unsaturated fatty acids such as Shea butter;
    • g) minerals such as sources of zinc, magnesium, and iron;
A second type of skin benefit agent is a skin conditioner used to provide a moisturized feel to the skin. Suitable skin conditioners include:
    • a) silicone oils, gums and modifications thereof such as linear and cyclic polydimethylsiloxanes, amino, alkyl, and alkyl aryl silicone oils;
    • b) hydrocarbons such as liquid paraffins, petrolatum, Vaseline, microcrystalline wax, ceresin, squalene, pristan, paraffin wax and mineral oil;
    • c) conditioning proteins such as milk proteins, silk proteins and glutens;
    • d) cationic polymers as conditioners which may be used include Quatrisoft LM-200 Polyquaternium-24, Merquat Plus 3330-Polyquaternium 30; and Jaguar® type conditioners;
    • e) humectants such as glycerol, sorbitol, and urea;
    • f) emollients such as esters of long chain fatty acids, such as isopropyl palmitate and cetyl lactate.
A third type of benefit agent is deep cleansing agents. These are defined here as ingredients that can either increase the sense of refreshment immediately after cleansing or can provide a sustained effect on skin problems that are associated with incomplete cleansing. Deep cleansing agents include:
    • a) antimicrobials such as 2-hydrozy-4,2′,4′-trichlorodiphenylether (DP300) 2,6-dimethyl-4-hydroxychlorobenzene (PCMX),3,4,4′-trichlorocarbanilide (TCC), 3-trifluoromethyl-4,4′-dichlorocarbanilide (TFC), benzoyl peroxide, zinc salts, tea tree oil,
    • b) anti-acne agents such as salicylic acid, lactic acid, glycolic acid, and citric acid, and benzoyl peroxide (also an antimicrobial agent),
    • c) oil control agents including sebum suppressants, modifiers such as silica, titanium dioxide, oil absorbers, such as micro sponges,
    • d) astringents including tannins, zinc and aluminum salts, plant extracts such as from green tea and Witch-hazel (Hammailes),
    • e) scrub and exfoliating particles, such as polyethylene spheres, agglomerated silica, sugar, ground pits, seeds, and husks such as from walnuts, peach, avocado, and oats, salts,
    • f) cooling agents such as methanol and its various derivatives and lower alcohols,
    • g) fruit and herbal extracts,
    • h) skin calming agents such as aloe vera,
    • i) essential oils such as mentah, jasmine, camphor, white cedar, bitter orange peel, rye, turpentine, cinnamon, bergamot, citrus unshiu, calamus, pine, lavender, bay, clove, hiba, eucalyptus, lemon, starflower, thyme, peppermint, rose, sage, menthol, cineole, sugenol, citral, citronelle, borneol, linalool, geranoil, evening primrose, camphor, tymol, spirantol, penene, limonene and terpenoid oils.
Other benefit agents that can be employed include antiaging compounds, sunscreens, and in lightening agents.
When the benefit agent is oil, especially low viscosity oil, it may be advantageous to pre-thicken it to enhance its delivery. In such cases, hydrophobic polymers of the type describe in U.S. Pat. No. 5,817,609 to He et al. may be employed, which is incorporated by reference into the subject application.
    • The final liquid cleanser composition of the present invention should have a viscosity more than 10,000 cps preferably greater than 20,000 cps and less than 500,000 cps measured at 0.5 rpm using Brookfield RVT Viscometer with Helipath Accessory; chuck, weight and closer assembly for T-bar Spindle A attachment and a plastic cups diameter greater than 2.5 inches at temperature 25° C.;
and pH of the liquid should be between 4.5 to 7.6, preferably 5.0 to 7.2. The compositions should also be physically phase stable at room temperature and 40° C. for at least two 2 weeks.
Other Optional Components
In addition, the compositions of the invention may include 0 to 10% by wt. optional ingredients as follows:
Perfumes; sequestering agents, such as tetra sodium ethylenediaminetetraacetate (EDTA), EHDP or mixtures in an amount of 0.01 to 1%, preferably 0.01 to 0.05%; and coloring agents, opacifiers and pearlizers such as zinc striate, magnesium stearate, T1O2, EGMS (ethylene glycol monostearate) or Lytron 621 (Styrene/Acrylate copolymer); all of which are useful in enhancing the appearance or cosmetic properties of the product.
The compositions may further comprise antimicrobials such as 2-hydroxy-4,2′4′ trichlorodiphenyl ether (DP300); preservatives such as dimethyloldimethylhydantoin (Glydant XL 1000), parabens, sorbic acid etc.
Antioxidants such as, for example, butylated hydroxytoluene (BHT) may be used advantageously in amounts of about 0.01% or higher if appropriate.
Polyethylene glycols as conditioners which may be used include:
Polyox WSR-25 PEG 14M,
Polyox WSR-N-60K PEG 45M, or
Polyox WSR-N-750 PEG 7M.
Another ingredient which may be included are exfoliants such as polyoxyethylene beads, walnut shells and apricot seeds.
Foaming by Solution Cylinder Shake Method:
  • 1. Mix 5 g of the liquid cleanser with 45 g of deionized water for about 5 minutes until it forms a uniform solution.
  • 2. Add 10 grams of the above diluted liquid cleanser solution to a 50 cc cylinder (about 24 cm high, 2.06 cm in diameter).
  • 3. Cap the cylinder with glass stopper, grape the top of the cylinder and shake the cylinder in a up and down motion with a distance about 20 to 30 cm 20 times within 8 to 12 sec.
  • 4. Once shaking is over, wait 60 seconds before taking the foam measurement.
  • 5. Measure the foam volume, which is defined as the volume from the surface of the solution to the top of the foam column.
  • 6. Repeat the run for total 4 times, the average foam volume with standard deviation for each liquid is calculated and shown in the tables.
EXAMPLES 1-3 AND COMPARATIVE EXAMPLES
The following examples 1 to 3 and comparatives A to E were prepared to demonstrate the invention.
Example of this invention
1 2 3 — — — — —
Comparative example
F
— — A B C C2 D E (Control)
Isethionate product A 2 2 2 2 2 4 2 2 —
Na cocoyl isethionate — — — — — — 4 — — —
Jordapon CI
Na cocoamido propyl 4 4 4 4 4 4 4 4 4 4
betaine
Na cocoyl glycinate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
Na laurylethoxyl sulfate 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
Lauric acid 1.5 0.81 — 2.3 2.9 1.5 1.5 4.0 0.5 1.5
ASAD* — 0.69 — 1.0 0.4 — — 0 1.0 —
Glycerin 1.15 1.15 1.15 1.15 1.15 1.15 1.15 1.15 1.15 1.15
Cationic polymer 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Aqua D4051
Sunflower seed oil 1 1 1 1 1 1 1 1 1 1
Petrolatum Penreco Snow 4 4 4 4 4 4 4 4 4 4
Pure Gel B990 starch 4 6 8 4 4 4 4 4 4 4
Perfume 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Total fatty acid/fatty soaps 2.25 2.25 0.70 4.05 4.05 2.9 1.74 4.70 2.25 1.5
Total fatty acid/fatty soaps 0.55 1.24 0.55 1.55 0.95 1.10 0.096 0.55 1.55 0
greater than or equal to C16
wt. %
Lather volume (cc) by Solution Cylinder Shake Method
Foam volume (cc) 42.5 41.4 40.1 23.5 30.0 33.3 42.5 28.5 37.3 38
44.5 42.5 40.4 24.7 29.4 30.8 41 28.2 37.4 35.5
41.5 43.6 41 22.7 25.8 30.2 44.5 26.4 36.7 36.5
45.0 40.5 43.1 25.0 27.9 31.2 40.5 25.2 37.0 38.5
Average foam volume (cc) 43.4 42 41.2 23.9 28.3 31.4 41.1 27.1 37.2 37.1
Standard deviation (cc) 1.37 1.05 0.98 0.87 1.43 0.96 1.37 1.28 0.3 1.1
ASAD: Mixture of 51% C18/49% C16 linear fatty acid.
The following examples 4-7 and comparatives G-3 were further prepared to demonstrate the invention.
Example of this invention
4 — 5 — 6 7 — —
Comparative example
— G — H — — I J
Isethionate product A 2 2 1 1 2 2 2 2
Na cocoamido propyl 0 0 4.8 4.8 4.8 4.8 4.8 4.8
betaine
Na cocoyl glycinate 2.7 2.7 4 4 4 4 4 4
Na laurylsarcosinate — — 1 1 1 1 1 1
Na laurylethoxyl sulfate 5.0 5.0 — — — — — —
Lauric acid 2.5 2.5 1.6 3.1 3.0 2.0 3.0 1.5
ASAD* — 0.8 0 0.6 — — 0.6 1.5
Glycerin 1.15 1.15 10 10 6 6 6 6
Cationic polymer — — 0.4 0.4 0.2 0.2 0.2 0.2
Lamberti BF Guar C17
Sunflower seed oil 1 1 — — — — — —
Petrolatum Penreco Snow 4 4 30 30 5 5 5 5
Pure Gel B990 starch — — 6 3 6 6 6 6
Carbopol C980 0.8 0.8 — — — — — —
Perfume 1.3 1.3 1.0 1.0 1 1 1 1
Total fatty acid/fatty soaps 3.25 4.05 1.95 4.05 3.70 2.70 4.30 3.70
Total fatty acid/fatty soaps 0.55 1.35 0.28 0.88 0.55 0.55 1.15 2.05
greater than or equal to
C16
Lather volume (cc) by Solution Cylinder Shake Method
41.0 27.5 48.0 36.2 43.0 46.5 28.1 34.0
41.7 24.9 43.5 32.8 43.0 45.0 28.0 34.7
38.5 25.8 44.5 36.0 44.5 42.5 26.3 32.2
37.0 27.8 46.2 34.0 44.5 44.5 31.5 34.1
Average foam volume 39.6 26.5 45.6 34.8 43.7 44.6 28.5 33.7
Standard deviation 1.8 1.15 1.55 1.35 0.75 1.13 1.51 0.78
ASAD: Mixture of 51% C18/49% C16 linear fatty acid.

Discussion
All examples in Table 1 and Table 2 were prepared by mixing all the ingredients except petrolatum, sunflower seed oil, perfume, glydant and EDTA at 70 to 75° C. for 30 to 50 minutes until all the solid ingredients such as isethionate product A and fatty acids dissolved to form an uniform mixture. Molten petrolatum and sunflower seed oil were added during cooling. Perfume and glydant plus (a hydantoin preservative) were added after the liquid was cooled below 40° C. Isethionate product A are fatty acyl isethionate products manufactured by Unilever. They contain about 50 wt % of fatty acyl isethionate surfactant with about 30% of the fatty acyl group equal to or longer than 16 carbon, and about 35 wt % of linear fatty acid/linear fatty soap in which about 79 wt % of the fatty acid/fatty soap have 16 to 20 carbons. The lather volume for each prepared sample measured using the solution shake method as set forth in the protocol is also summarized in Tables 1 and 2.
Comparative example F (Control), a liquid without any fatty acyl isethionate product, was prepared as control for lather volume comparison. It can be seen clearly in Examples 1, 2 and 3 versus comparative F that addition of fatty acyl isethionate product at low level (2% isethionate product A) enhances foam volume (e.g., from 37.1 to about 42 on average). However, when higher level, i.e. 4%, of the preferred fatty acyl isethionate product is added (Comparative example C), foam volume is depressed (31.4) compared to comparative F which contains no fatty acyl isethionate product. This happens only for the preferred fatty acyl isethionate product of this invention. Addition of 4% Jordapon, Na cocoyl isethionate product containing about 6% free coconut fatty acid and about 85% of fatty acyl isethionate surfactant with about 18% of the fatty acyl group equal to or longer than 16 carbons, shows an enhancement of foam volume as shown in comparative C2. However, since C2 has less % of >C16 fatty acid and fatty acyl isethonate, it would not have good mildness.
Again, comparing Examples 3, 4, 5 and 6 to Comparatives G, H, I and J, it is seen that keeping total fatty acid/fatty soap level low (<4%) is critical. In all inventive examples, foam (at >40 cc absolute values) is significantly better.)

Claims (2)

What is claimed is:
1. A personal liquid cleansing composition comprising:
(a) 0.3 to less than 4% by wt. fatty acyl isethionate product comprising 40 to 80% fatty acyl isethionate and 15% to 50% free fatty acid and/or soap wherein greater than 20% of the fatty acyl isethionate are of chain length greater than or equal to C16 and greater than 50% of the free fatty acid/soap is of chain length greater than or equal to C16 to C24;
(b) 3 to 15% by wt. of a co-surfactant selected from the group consisting of anionic surfactant, amphoteric surfactant, nonionic surfactant, and mixtures thereof wherein said anionic surfactant excludes fatty acyl isethionate product of (a);
(c) 0.1 to less than 4% C8 to C20 total linear free fatty acids/fatty soap wherein said total linear free fatty acids/fatty soap includes both free fatty acids/fatty soaps of fatty acyl isethionate product (a) as well as those added separately in composition;
wherein total amount of linear C16 to C20 fatty acids is less than 1.5%, but is at least 0.1% by wt; and
wherein the ration of fatty acyl isethionate surfactant of (a) to total synthetic surfactant (b) is less than 1 to 2; wherein foam value of composition (measured by cylinder shake shake method with total fatty acid/soap level less than 4% is better by at least 10% , relative to identical composition comprising greater than or equal to 4% total fatty acids/soap.
2. A composition according to claim 1 having pH of 4.5 to 7.6.
US12/577,425 2009-10-12 2009-10-12 Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content Active 2029-12-19 US8124574B2 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US12/577,425 US8124574B2 (en) 2009-10-12 2009-10-12 Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content
EP10760681.6A EP2498747B1 (en) 2009-10-12 2010-10-01 Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content
JP2012533566A JP5941408B2 (en) 2009-10-12 2010-10-01 Less irritating foaming liquid detergent comprising low level fatty isethionate product and low content of total fatty acids and / or fatty acid soap
BR112012007254-4A BR112012007254B1 (en) 2009-10-12 2010-10-01 personal cleaning liquid composition
EA201290196A EA021866B1 (en) 2009-10-12 2010-10-01 Liquid cleanser comprising acylisethionate product
ES10760681.6T ES2529710T3 (en) 2009-10-12 2010-10-01 Soft liquid foaming cleansers comprising low levels of a fatty isethionate product and a low content of total fatty acids and / or fatty acid soap
PCT/EP2010/064629 WO2011045191A2 (en) 2009-10-12 2010-10-01 Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content
CA2774287A CA2774287C (en) 2009-10-12 2010-10-01 Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content
MX2012004296A MX2012004296A (en) 2009-10-12 2010-10-01 Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content.
CN201080045859.4A CN102939071B (en) 2009-10-12 2010-10-01 Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content
ARP100103671A AR078567A1 (en) 2009-10-12 2010-10-08 LIQUID CLEANERS THAT FORM FOAM, SOFT, THAT INCLUDE LOW LEVELS OF ISETIONATE PRODUCT FAT AND LOW TOTAL CONTENT OF FATTY ACID AND / OR SOAP OF ACID FAT
ZA2012/01631A ZA201201631B (en) 2009-10-12 2012-03-05 Mild,foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US12/577,425 US8124574B2 (en) 2009-10-12 2009-10-12 Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content

Publications (2)

Publication Number Publication Date
US20110086789A1 US20110086789A1 (en) 2011-04-14
US8124574B2 true US8124574B2 (en) 2012-02-28

Family

ID=43755147

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/577,425 Active 2029-12-19 US8124574B2 (en) 2009-10-12 2009-10-12 Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content

Country Status (12)

Country Link
US (1) US8124574B2 (en)
EP (1) EP2498747B1 (en)
JP (1) JP5941408B2 (en)
CN (1) CN102939071B (en)
AR (1) AR078567A1 (en)
BR (1) BR112012007254B1 (en)
CA (1) CA2774287C (en)
EA (1) EA021866B1 (en)
ES (1) ES2529710T3 (en)
MX (1) MX2012004296A (en)
WO (1) WO2011045191A2 (en)
ZA (1) ZA201201631B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9193942B2 (en) 2012-11-30 2015-11-24 Danielle D Manning Soap recycling and conversion process
US9242002B2 (en) 2010-08-18 2016-01-26 Conopco, Inc. Anti-dandruff shampoo
US9526684B2 (en) 2014-08-25 2016-12-27 Galaxy Surfactant, Ltd. Isotropic, flowable, skin pH aqueous cleansing compositions comprising N-acyl glycinates as primary surfactants
EP2882410B1 (en) 2013-05-08 2017-09-27 Galaxy Surfactants Limited Blends of o-acyl isethionates and n- acyl amino acid surfactants
US11484488B2 (en) 2018-07-26 2022-11-01 The Procter & Gamble Company Personal cleansing compositions

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA021919B9 (en) * 2010-03-31 2016-03-31 Унилевер Н.В. Personal wash cleanser with mild surfactant systems comprising defined alkanoyl chemical compounds and defined fatty acyl isethionate surfactant product and optional skin or hair benefit agent
US8105994B2 (en) * 2010-03-31 2012-01-31 Conopco, Inc. Personal wash cleanser comprising defined alkanoyl compounds, defined fatty acyl isethionate surfactant product and skin or hair benefit agent delivered in flocs upon dilution
US8105995B2 (en) * 2010-05-05 2012-01-31 Conopco, Inc. Specific mild low surfactant, high emollient systems which retain foaming and phase stability
US8114824B1 (en) * 2010-12-06 2012-02-14 Conopco, Inc Compositions comprising fatty acyl isethionate surfactant product, alkanoyl compounds and triglycerides with low level of hydrogenation
FR3012962B1 (en) * 2013-11-13 2016-07-15 Oreal FOAMING COMPOSITION COMPRISING AT LEAST ONE SURFACTANT OF GLYCINATE TYPE
JP7063556B2 (en) 2017-07-04 2022-05-09 ロレアル Foaming cleanser

Citations (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723325A (en) 1967-09-27 1973-03-27 Procter & Gamble Detergent compositions containing particle deposition enhancing agents
GB2015561A (en) 1978-03-06 1979-09-12 Unilever Ltd Liquid soap compositions
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
US5009814A (en) 1987-04-08 1991-04-23 Huls Aktiengesellschaft Use of n-polyhydroxyalkyl fatty acid amides as thickening agents for liquid aqueous surfactant systems
US5132037A (en) 1989-05-05 1992-07-21 Lever Brothers Company, Division Of Conopco, Inc. Aqueous based personal washing cleanser
US5234619A (en) 1989-05-05 1993-08-10 Lever Brothers Company, Division Of Conopco, Inc. Aqueous based personal washing cleanser
EP0559375A1 (en) 1992-02-27 1993-09-08 Unilever Plc Cleansing composition
US5372751A (en) 1990-02-09 1994-12-13 Lever Brothers Company, Division Of Conopco, Inc. Acyl isethionate skin cleaning compositions containing betaines, amido sulfosuccinates or combinations of the two
US5389279A (en) 1991-12-31 1995-02-14 Lever Brothers Company, Division Of Conopco, Inc. Compositions comprising nonionic glycolipid surfactants
US5415810A (en) 1991-11-05 1995-05-16 Lever Brothers Company, Division Of Conopco, Inc. Detergent composition
WO1997005957A1 (en) 1995-08-04 1997-02-20 The Black Clawson Company Forward or reverse hydrocyclone systems and methods
US5612307A (en) 1994-07-19 1997-03-18 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing separate stripes of surface active agents and benefit agent
US5716919A (en) 1995-05-09 1998-02-10 The Andrew Jergens Company Mild cleansing formulation with a hydroxy-containing compound, a nonionic surfactant and an anionic surfactant
US5739365A (en) 1991-06-26 1998-04-14 Ppg Industries, Inc. Method for preparing ammonium hydroxyalkyl sulfonates and ammonium alkanoyl alkyl sulfonates produced therefrom
US5804540A (en) 1997-01-08 1998-09-08 Lever Brothers Company, Division Of Conopco, Inc. Personal wash liquid composition comprising low viscosity oils pre-thickened by non-antifoaming hydrophobic polymers
WO1999032069A2 (en) 1997-12-18 1999-07-01 Unilever Plc Liquid composition with enhanced low temperature stability
US5952286A (en) 1995-08-07 1999-09-14 Lever Brothers Company Liquid cleansing composition comprising soluble, lamellar phase inducing structurant and method thereof
US5965500A (en) 1997-07-24 1999-10-12 Levers Brothers Company, Division Of Conopco, Inc. Stable liquid composition comprising high levels of emollients
WO2000021492A2 (en) 1998-10-13 2000-04-20 Johnson And Johnson Consumer Companies, Inc. Cream cleanser with high levels of emollients and glycerin
US6077816A (en) 1995-08-07 2000-06-20 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Liquid cleansing composition comprising soluble, lamellar phase inducing structurant
EP1029532A1 (en) 1999-02-17 2000-08-23 Unilever Plc Liquid cleansing composition
US6429177B1 (en) 2000-08-22 2002-08-06 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Separating multi-phase personal wash composition in a transparent or translucent package
EP1237534A1 (en) 1999-12-06 2002-09-11 Unilever Plc Stable, high glycerol liquids comprising sulfosuccinic acid monoesters
WO2003017968A2 (en) 2001-08-24 2003-03-06 Unilever Plc Lamellar post foaming cleansing composition and dispensing system
US20040224863A1 (en) 2003-05-08 2004-11-11 Sun James Ziming Liquid detersive composition containing sodium cocoyl isethionate
EP1479365A1 (en) 2003-05-22 2004-11-24 Unilever Plc Personal product composition comprising a structured benefit agent composition and a delivery vehicle
US20050075256A1 (en) 2003-08-28 2005-04-07 Joseph Librizzi Methods of reducing irritation associated with personal care compositions
US20050100570A1 (en) 2003-05-08 2005-05-12 The Procter & Gamble Company Multi-phase personal care composition
US20050136026A1 (en) 2003-12-23 2005-06-23 Qiang Qiu Ordered liquid crystalline cleansing composition with C16-24 normal monoalkylsulfosuccinates and C16-24 normal alkyl carboxylic acids
US20050143268A1 (en) 2003-11-14 2005-06-30 The Procter & Gamble Company Personal care composition containing a cleansing phase and a benefit phase
US20050192188A1 (en) 2004-02-27 2005-09-01 Wagner Julie A. Mild body wash
US20060079420A1 (en) 2004-10-08 2006-04-13 Wagner Julie A Multi-phase personal cleansing composition
WO2006077495A1 (en) 2005-01-24 2006-07-27 Pronova Biocare As Use of a fatty acid composition containing dha for the production of a medical product or a food stuff for the treatment of amyloidos-rerelated diseases
US7084104B2 (en) 2003-08-28 2006-08-01 Johnson & Johnson Consumer Company Inc. Mild and effective cleansing compositions
US7098180B2 (en) 2003-08-28 2006-08-29 Johnson & Johnson Consumer Companies Inc. Mild and effective cleansing compositions
US7119059B2 (en) 2003-08-28 2006-10-10 Johnson & Johnson Consumer Companies, Inc. Mild and effective cleansing compositions
WO2008074617A1 (en) 2006-12-20 2008-06-26 Unilever Plc Stable liquid cleansing compositions comprising fatty acyl isethionate surfactants
WO2009030594A1 (en) 2007-09-05 2009-03-12 Unilever Plc Stable liquid cleansing compositions containing fatty acyl isethionate surfactant
US20090156450A1 (en) * 2007-12-18 2009-06-18 Conopco, Inc., D/B/A Unilever Fatty acyl isethionate product-containing liquid cleansing compositions stabilized with mixture of long chain and short chain fatty acids/fatty soaps
US7655607B2 (en) 2006-12-20 2010-02-02 Conopco, Inc. Method of providing stability for liquid cleansing compositions comprising selection fatty acyl isethionate surfactants
US7671000B2 (en) 2006-12-20 2010-03-02 Conopco, Inc. Stable liquid cleansing compositions comprising fatty acyl isethionate surfactant products with high fatty acid content

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4585647A (en) * 1984-11-19 1986-04-29 Basf Corporation Methods and compositions for intravaginal contraception
US5817609A (en) 1997-01-08 1998-10-06 Lever Brothers Company, Division Of Conopco, Inc. Bar composition comprising low viscosity oils pre-thickened by non-antifoaming hydrophobic polymers
US20050136020A1 (en) * 2003-12-19 2005-06-23 Ginger King Silicone-free long-lasting shine hair care compositions

Patent Citations (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723325A (en) 1967-09-27 1973-03-27 Procter & Gamble Detergent compositions containing particle deposition enhancing agents
GB2015561A (en) 1978-03-06 1979-09-12 Unilever Ltd Liquid soap compositions
US4565647A (en) 1982-04-26 1986-01-21 The Procter & Gamble Company Foaming surfactant compositions
US4565647B1 (en) 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
US5009814A (en) 1987-04-08 1991-04-23 Huls Aktiengesellschaft Use of n-polyhydroxyalkyl fatty acid amides as thickening agents for liquid aqueous surfactant systems
US5132037A (en) 1989-05-05 1992-07-21 Lever Brothers Company, Division Of Conopco, Inc. Aqueous based personal washing cleanser
US5234619A (en) 1989-05-05 1993-08-10 Lever Brothers Company, Division Of Conopco, Inc. Aqueous based personal washing cleanser
US5290471A (en) 1989-05-05 1994-03-01 Lever Brothers Company, Division Of Conopco, Inc. Aqueous based personal washing cleanser
US5372751A (en) 1990-02-09 1994-12-13 Lever Brothers Company, Division Of Conopco, Inc. Acyl isethionate skin cleaning compositions containing betaines, amido sulfosuccinates or combinations of the two
US5739365A (en) 1991-06-26 1998-04-14 Ppg Industries, Inc. Method for preparing ammonium hydroxyalkyl sulfonates and ammonium alkanoyl alkyl sulfonates produced therefrom
US5415810A (en) 1991-11-05 1995-05-16 Lever Brothers Company, Division Of Conopco, Inc. Detergent composition
US5389279A (en) 1991-12-31 1995-02-14 Lever Brothers Company, Division Of Conopco, Inc. Compositions comprising nonionic glycolipid surfactants
EP0559375A1 (en) 1992-02-27 1993-09-08 Unilever Plc Cleansing composition
US5612307A (en) 1994-07-19 1997-03-18 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing separate stripes of surface active agents and benefit agent
US5716919A (en) 1995-05-09 1998-02-10 The Andrew Jergens Company Mild cleansing formulation with a hydroxy-containing compound, a nonionic surfactant and an anionic surfactant
WO1997005957A1 (en) 1995-08-04 1997-02-20 The Black Clawson Company Forward or reverse hydrocyclone systems and methods
US5952286A (en) 1995-08-07 1999-09-14 Lever Brothers Company Liquid cleansing composition comprising soluble, lamellar phase inducing structurant and method thereof
US6077816A (en) 1995-08-07 2000-06-20 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Liquid cleansing composition comprising soluble, lamellar phase inducing structurant
US5804540A (en) 1997-01-08 1998-09-08 Lever Brothers Company, Division Of Conopco, Inc. Personal wash liquid composition comprising low viscosity oils pre-thickened by non-antifoaming hydrophobic polymers
US5965500A (en) 1997-07-24 1999-10-12 Levers Brothers Company, Division Of Conopco, Inc. Stable liquid composition comprising high levels of emollients
WO1999032069A2 (en) 1997-12-18 1999-07-01 Unilever Plc Liquid composition with enhanced low temperature stability
WO2000021492A2 (en) 1998-10-13 2000-04-20 Johnson And Johnson Consumer Companies, Inc. Cream cleanser with high levels of emollients and glycerin
EP1029532A1 (en) 1999-02-17 2000-08-23 Unilever Plc Liquid cleansing composition
EP1237534A1 (en) 1999-12-06 2002-09-11 Unilever Plc Stable, high glycerol liquids comprising sulfosuccinic acid monoesters
US6429177B1 (en) 2000-08-22 2002-08-06 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Separating multi-phase personal wash composition in a transparent or translucent package
WO2003017968A2 (en) 2001-08-24 2003-03-06 Unilever Plc Lamellar post foaming cleansing composition and dispensing system
US20050100570A1 (en) 2003-05-08 2005-05-12 The Procter & Gamble Company Multi-phase personal care composition
US20040224863A1 (en) 2003-05-08 2004-11-11 Sun James Ziming Liquid detersive composition containing sodium cocoyl isethionate
EP1479365A1 (en) 2003-05-22 2004-11-24 Unilever Plc Personal product composition comprising a structured benefit agent composition and a delivery vehicle
US20050075256A1 (en) 2003-08-28 2005-04-07 Joseph Librizzi Methods of reducing irritation associated with personal care compositions
US7098180B2 (en) 2003-08-28 2006-08-29 Johnson & Johnson Consumer Companies Inc. Mild and effective cleansing compositions
US7119059B2 (en) 2003-08-28 2006-10-10 Johnson & Johnson Consumer Companies, Inc. Mild and effective cleansing compositions
US7084104B2 (en) 2003-08-28 2006-08-01 Johnson & Johnson Consumer Company Inc. Mild and effective cleansing compositions
US20050143268A1 (en) 2003-11-14 2005-06-30 The Procter & Gamble Company Personal care composition containing a cleansing phase and a benefit phase
US20050136026A1 (en) 2003-12-23 2005-06-23 Qiang Qiu Ordered liquid crystalline cleansing composition with C16-24 normal monoalkylsulfosuccinates and C16-24 normal alkyl carboxylic acids
US20050192188A1 (en) 2004-02-27 2005-09-01 Wagner Julie A. Mild body wash
US20060079420A1 (en) 2004-10-08 2006-04-13 Wagner Julie A Multi-phase personal cleansing composition
WO2006077495A1 (en) 2005-01-24 2006-07-27 Pronova Biocare As Use of a fatty acid composition containing dha for the production of a medical product or a food stuff for the treatment of amyloidos-rerelated diseases
WO2008074617A1 (en) 2006-12-20 2008-06-26 Unilever Plc Stable liquid cleansing compositions comprising fatty acyl isethionate surfactants
US7655607B2 (en) 2006-12-20 2010-02-02 Conopco, Inc. Method of providing stability for liquid cleansing compositions comprising selection fatty acyl isethionate surfactants
US7659235B2 (en) 2006-12-20 2010-02-09 Conopco, Inc. Stable liquid cleansing compositions which may be prepared using fatty acyl isethionate surfactants
US7671000B2 (en) 2006-12-20 2010-03-02 Conopco, Inc. Stable liquid cleansing compositions comprising fatty acyl isethionate surfactant products with high fatty acid content
WO2009030594A1 (en) 2007-09-05 2009-03-12 Unilever Plc Stable liquid cleansing compositions containing fatty acyl isethionate surfactant
US7674759B2 (en) 2007-09-05 2010-03-09 Conopco, Inc. Stable liquid cleansing compositions containing high level of fatty acid isethionate surfactant products having more than 10 wt. % of fatty acid/fatty soap content
US20090156450A1 (en) * 2007-12-18 2009-06-18 Conopco, Inc., D/B/A Unilever Fatty acyl isethionate product-containing liquid cleansing compositions stabilized with mixture of long chain and short chain fatty acids/fatty soaps
US7807612B2 (en) 2007-12-18 2010-10-05 Conopco, Inc. Fatty acyl isethionate product-containing liquid cleansing compositions stabilized with mixture of long chain and short chain fatty acids/fatty soaps

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
Co-pending application for: Applicant: Tsaur et al.; U.S. Appl. No. 12/235,955, filed Sep. 23, 2008; entitled: Stable cleansing compositions containing fatty acyl isethionoate surfactant products having more than 10 wt. % of fatty acid/fatty soap content using high level of polyol and methods thereof.
Co-pending application for: Applicant: Tsaur et al.; U.S. Appl. No. 12/751,063, flied Mar. 31, 2010; entitled Personal wash cleanser comprising defined alkanoyl compounds, defined fatty acyl isethionate surfactant product and skin of hair benefit agent.
Co-pending application for: Applicant: Tsaur et al.; U.S. Appl. No. 12/751,079, filed Mar. 31, 2010; entitled: Personal wash cleanser comprising defined alkanoyl compounds, defined fatty acyl isethionate surfactant product and skin or hair benefit a ant delivered in flocs upon dilution.
Co-pending application for: Applicant: Tseur et al.; U.S. Appl. No. 12/751,049, filed Mar. 31, 2010: entitled: Personal wash cleanser with mild surfactant systems comprising defined alkartoyi compounds and defined fatty acyl isethionate surfactant product.
PCT International Search Report and Written Opinion on Application No. PCT/EP2010/064629 dated Apr. 27, 2011.
PCT Search Report and Written Opinion for Internationai Application No. PCT/EP2009/062278 dated Sep. 22, 2009.
PCT Search Report on International Application No. PCT/EP2008/060835 dated Jan. 26, 2009.
PCT Search Report on International Application No. PCT/EP2008/067530 dated Jul. 24, 2009.
PCT Search Report on International Application No. PCTIEP2007/063128 dated Apr. 15, 2008.
XP-002474464, Oct. 1988, Engiish translation of JP 1987-0077976 (based on JP 63-243200).

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9242002B2 (en) 2010-08-18 2016-01-26 Conopco, Inc. Anti-dandruff shampoo
US9193942B2 (en) 2012-11-30 2015-11-24 Danielle D Manning Soap recycling and conversion process
EP2882410B1 (en) 2013-05-08 2017-09-27 Galaxy Surfactants Limited Blends of o-acyl isethionates and n- acyl amino acid surfactants
US9526684B2 (en) 2014-08-25 2016-12-27 Galaxy Surfactant, Ltd. Isotropic, flowable, skin pH aqueous cleansing compositions comprising N-acyl glycinates as primary surfactants
US11484488B2 (en) 2018-07-26 2022-11-01 The Procter & Gamble Company Personal cleansing compositions
US11638683B2 (en) 2018-07-26 2023-05-02 The Procter & Gamble Company Personal cleansing compositions

Also Published As

Publication number Publication date
ES2529710T3 (en) 2015-02-24
WO2011045191A2 (en) 2011-04-21
US20110086789A1 (en) 2011-04-14
EA201290196A1 (en) 2012-10-30
EA021866B1 (en) 2015-09-30
ZA201201631B (en) 2013-05-29
BR112012007254B1 (en) 2020-12-29
CA2774287C (en) 2017-08-22
JP5941408B2 (en) 2016-06-29
BR112012007254A2 (en) 2020-08-11
CA2774287A1 (en) 2011-04-21
EP2498747B1 (en) 2014-12-03
EP2498747A2 (en) 2012-09-19
WO2011045191A3 (en) 2011-06-23
JP2013507412A (en) 2013-03-04
CN102939071B (en) 2014-07-30
CN102939071A (en) 2013-02-20
AR078567A1 (en) 2011-11-16
MX2012004296A (en) 2012-05-22

Similar Documents

Publication Publication Date Title
US8124574B2 (en) Mild, foaming liquid cleansers comprising low levels of fatty isethionate product and low total fatty acid and/or fatty acid soap content
EP2182913B1 (en) Stable liquid cleansing compositions containing fatty acyl isethionate surfactant
US7879780B2 (en) Stable cleansing compositions containing fatty acyl isethionate surfactant products having more than 10 wt. % of fatty acid/fatty soap content using high level of polyol and methods thereof
US7659235B2 (en) Stable liquid cleansing compositions which may be prepared using fatty acyl isethionate surfactants
US7671000B2 (en) Stable liquid cleansing compositions comprising fatty acyl isethionate surfactant products with high fatty acid content
US7655607B2 (en) Method of providing stability for liquid cleansing compositions comprising selection fatty acyl isethionate surfactants
US7807612B2 (en) Fatty acyl isethionate product-containing liquid cleansing compositions stabilized with mixture of long chain and short chain fatty acids/fatty soaps
EP3972558A1 (en) Lamellar liquid cleansers comprising acyl isethionate and methyl acyl taurate surfactant mixtures
RU2812260C2 (en) Lamellar liquid cleansers containing mixtures of surfactants acylisethionate and methylacyltaurate

Legal Events

Date Code Title Description
AS Assignment

Owner name: CONOPCO, INC., D/B/A/ UNILEVER, NEW JERSEY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TSAUR, LIANG SHENG;VILLA, VIRGILIO BARBA;REEL/FRAME:023443/0284

Effective date: 20091022

STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 12